Composition comprising ice color coupling components



inconvenience.

Patented Nov. 2 5, 1941 COMPOSITION COMPRISING ICE COLOR COUPLINGCOMPONENTS Miles A. Dahlen, Wilmington, Del., and Arthur L.

Fox, Woodstown, N. J., assignors to E. I.

du Pont de Nemours & Company, Wilmington,

DeL, a corporation of Delaware No Drawing. Application August 9, 1939,

' Serial No. 289,182

6 Claims.

This invention relates to dispersible solubilized compositionscontaining azo dye intermediates which are devoid of sulfonic acidand'carboxylic acid groups, such as the class of which the arylamides of2:3-hydroxy-naphthoic acid are representative, and to new compositionsof matter useful in printing which includes those dispersiblesolubilized intermediates.

These intermediates are generally knownas ice color coupling componentsand they are extensively used in the making of developed dyeings. Onedifficulty encountered'in the making of developed dyes with thesecoupling components is that the coupling components are largelyinsoluble in the ordinary dye bath and they must be first brought intosolution in a bath containing an excess of caustic soda. The developedcolors have been applied in various ways but they are usually applied byimpregnating the entire fabric with one component of the dye, developingby printing onto the fabric in the selected design with a printing pastecontaining the other component, and then removing the an atmosphericdrum drier in order to obtain a flaked or granular product and, whenthis is done, the sodiumsalt of Turkey red'B'il is preferred. Thiscomposition is readily soluble in aqueous sodium hydroxide solutions. Anexcess of alkali over'that required to form the sodium salt is commonlyrequired in the composition to excess of the first intermediate bysoaping and washing. The excess of caustic soda in the solution of thecoupling component presented an When arylamides, such as an arylamide of2,3-hydroxy-naphthoic acid were mixed with diazoimino compounds, theyhad to be wet out with an agent, such as alcohol, "Cellosolve or someother active solvent before they could be dissolved in caustic sodasolution. The wetting out of the coupling component was an operationwhich was desirable to avoid.

According to the present invention the wetting out of the couplingcomponent in the compounding of a printing paste is avoided. Thepresence of an undesirable excess of caustic soda in a pastewhich'contains both components of the dye is also avoided. In making adyeing the 40 Turkey red oil, a dispersing agent such as the 5condensation product of formaldehyde and naphthalene beta sulfonic acid,subjecting the mixture to milling so as to attain uniformity, drying,and subdividing to selected fineness. It

make the product instantly soluble. It is frequently desirable from thepoint of view of health to include only enough alkali to produce aturbid suspension. The turbidity of the suspension can then be removedby adding alkali to the bath. The preferred composition of matter ofthis invention, consequently, comprises a coupling component of the typedescribed, or the alkali metal salt thereof, alkali, dextrin or thesodium salt of Turkey red oil, and a dispersing agent. The preferredprocess comprises mixing these components and subjecting them to plasticmilling or drying on an atmospheric drum drier.

If a complete composition useful in printing is desired, an alkalistable diazoimino compound is included in the mixture.

Where the free acid form of certain favorable ice color couplingcomponents is used, no alkali is added, and the products wet out anddisperse in water rapidly to produce turbid suspensions. Addition ofalkali to these suspensions produces clear solutions of the alkali saltsof the ice color coupling components. Where the alkali metal salt of theice color coupling component is used, the products exhibit similarbehavior, producing turbid solutions containing both the ice colorcoupling components in the free state and alkali metal salts if littlealkali is added. Clear solutions are produced at once if sufiicientalkali is included.

The class of ice color coupling components to which this. invention isparticularly applicable ortho hydroxy-aryl-carboxylic acids, and to theis the arylamides of 2:3-hydroxy-naphthoic acid, which constitutes apreferred class. The invention is also applicable to the arylamides ofother arylamides of beta-keto-carboxyiic acids. In the followingexamples only the preferred class of arylamides of2-:3-hydroxy-naphthoic acid are used. However, the processes are equallyapplicable to the preparation of dispersibie and/or soluble compositionsfrom all other ice color coupling components, examples of which are thearylamides of 2-hydroxy-carbafiole-3-carboxylicacid, 7 hydroxyalpha-naphtho-carbazole 6- carboxylic-acid,2-hydroxy-anthracene-3-carboxylic-acid, and2-hydroxy-diphenylene-oxide-3- is frequently preferred to dry thecompound on carboxylic acid, arylamides of acyi-acetic-acids andtere-phthaloyl-bis-acetic-acids, amino-naphthols, andacylamino-naphthols. Examples of particular coupling components whichgive products quite as satisfactory as those listed in the examples are:

1- (2' :3-hydroxy naphthoylamino) 4 methylbenzene1-(2':3-hydroxy-naphthoylamino) 2:4-dimethyl-benzene 1-(2':3-hydroxy-naphthoylamino) -2 methoxybenzene l- (2':3'-hydroxy-naphthoylamino) -4 methoxy benzene l- (2:3-hydroxy-naphthoylamino) 2 :5-dimeth- Dl-4:'-(2":3"-hydroxy-naphthoylamino)1-3:3'-

dimethoxy-diphenyl. Y

If the composition is to be dried on a drum drier the sodium salt ofTurkey redoil should be used, but if other methods of drying are to beused dextrin is preferred. Any of the dextrins can be used. 7 Certainassistants to dextrin, such.

as sugar, can also be employed.

The dispersing agents used are those custoaaeaeie marily employed in theart for the dispersing V of dyes. The condensation product offormaldehyde and naphthalene-beta-sulfonic acid is particularlysatisfactory, but any such dispers- 7 'ing agent can be used.

The composition must be a uniform mixture such as a mixture producibleby plastic milling.

By "plastic milling is meant the subjection of the mass, todisintegration by internal world However, any mixing'of the componentswhich produces a uniform composition is satisfactory.

By drying the composition on an atmospheric drum drier flakes may beproduced which have the advantage of eliminating dust and all itsattending disadvantages from the dye house.

The following examples illustrate the invention but do not limit it. Allquantities are stated in parts by weight.

Example I A mixture of 49 parts of dextrin and 2 parts of thecondensation product of naphthalene-betasulfonic acid with formaldehydewas placed in -a Werner and Pfleiderer mixer and made into a smoothpaste by mixing with 30 parts of water.

To this paste was added 49- parts of 2-(2':3'-hydroxy-naphthoyl-amino)-naphthalene and the resulting plastic mass was milled for one hour.Additional water (10 parts) was added during the milling to replace partof that lost by evaporation due to the heating up of the plasticmixture. The well-mixed product was removed from the mixer, dried in avacuum oven, and coarsely ground. The virtually-dry product wet out anddispersed readily in water, forming a turbid suspension which dissolvedcompletely when heated in the presence of caustic soda.

F 'ree arylamides of 2:3-hydroxy-naphthoic naphthoic acid protects themfrom decomposi- 4 5 tion over reasonable periods of time and the mix- Ious suspension.

acid described in the prior art do not wet out and disperse in water. Ineveryone they must first be made into a paste with a wetting out agent,such asan alcohol or a. sulfonated castor oil derivative, before anaqueous dispersion can beobtained.

Erample II 2' :3' -hydroxy-naphthoyl-amino benzene (40 parts)wasstirredtoasmoothpastewith20 parts of ethyl alcohol. This paste wasdiluted with 40 parts of water and transferred from the mixing vessel toa vacuum graining bowl. Dextrin (29 parts). p wdered cane sugar (28parts).

and the condensation product from naphthalenebeta-sulfonic acid andformaldehyde (3 parts) were added and the mixture agitated untiluniform. Water was removed by warming the mixture under vacuum until aviscous, plastic mass was obtained. Thismass was agitated underatmospheric pressure, for one hour, and then dried by warming andapplying vacuum. The dried product was removed from the graining bowland coarsely ground. 7

The product so obtained wet out and dispersed readily in water anddissolved .to' a clear solution on addition of caustic soda to theresulting aque- Erample III 2- (2' :3"-hydroxy-naphthoyl-amino)naphthalene (34 parts) wasstlrredtoasmoothpaste with 20 parts of ethylalcohol and converted to its sodium salt by addition of 34 parts of 36B. caustic soda solution. This mixture was transferred from the mixingvessel to a vacuum grain- "ing bowl. The alcohol was removed'by warmingslightly and applying vacuum. The residue was diluted with 40 parts ofwater and then dextrin (2'! parts), powdered cane sugar (26 parts), and9. agent (3 parts of the condensation product of formaldehyde andnaphthalene-betasulfonic acid) were added. This mixture was agitated andthe excess water removed'by warming under vacuum. The resulting rmous.plastic mass was groimd by plastic milling under atmospheric pressurefor one hour and tuen dried by warming and applying vacuum. The driedproduct was removed from the graining bowl and coarsely ground. Whenadded to water this product rapidly wet out and dispersed. Upon additionof a small amount of alkali complete solution was rapidly obtained.

In the making of a composition for application to and development on afabric, a diazoimino compound, such as the compound made byreacting'piperidine-alpha-carboxylic acid with 4-chloro-2-amino-toluene, is added to the'mixture after it has been'wellmixed with alkali and the plastic milling is continued. 'Theresultingdried product is made into a paste in the usual way with starchtragacanth thickener, applied to a roll and by a roll to the fabric. Theprinted fabric is subjected to hot acetic acid vapors which overcome thealkalinity of the composition and permit coupling on the fiber. Materialprepared by this procedure wets out and dissolves completely in-hotdilute caustic soda solution.

2':3'-hydroxy-naphthoyl-amino-benzene processed by the above procedureyields a product which dissolves completely in water without theaddition of more caustic soda solution.

The presence of dextrin in these mixtures of alkali metal salts ofarylamides of 2:3-hydr'oxypattern of good brilliance and Products of theprior art neither exhibit the ease of solubility shown by these productsnor involve the use of a protective agent.

Example IV 1- (2' :3 hydnoxy naphthoyl amino) -naph-' thalene (34 parts)was stirred to a smooth paste with 20 parts of ethyl alcohol andconverted to a sodium salt by addition of 34 parts 01' 36 B.

1- (2 3' -hydroxy-naphthoyl-amino) -2-ethoxybenzene (40 parts) wasStirred to a smooth paste with 25 parts of ethyl alcohol and the pastewas diluted by the addition of 135 parts of a 30% 2,263,616 'tures wetout and disperse rapidly in water.

solution of an assistant; such as the condensation product ofbeta-naphthalene-sulfonic acid with formaldehyde. This suspension wasfurther diluted by the addition of a solution of 15 parts of dextrin and8 parts of powdered cane sugar in 50 parts of water. The suspension wasthoroughly mixed and then dried on a rotary drum drier. The product wetout rapidly in water and dissolved to a clear solution in dilute,aqueous caustic soda solution.

Example VI A water-soluble composition of matter suitable for theproduction of dyes on the fiber was prepared by mixing a dispersible icecolor coupling component of this invention with a water-solublediazoimino. or diazoamino compound in approximately equimolecularproportions. Such a composition consising of 100 parts'of thedispersible sodium salt of1-(2':3'-hydroxy-naphthoylamino)-2-methyl-benzene of 40% strength and 40parts of a diazoimino compound, obtained by reacting the diazo compoundfrom 4-chloro-2- amino-toluene with piperidine-alpha carboxylic acid wascompletely soluble in hot water. An aqueous solution of the abovemixture was added to neutral starch gum tragacanth' thickener andprinted on cotton cloth. The printedmaterial was dried and thensubjected to steam and acetic acid fumes for a short period. A redprinted fastness was obtained.

Example VII Example VIII 2'z3' hydroxynaphthoylamino benzene (50 parts)was mixed with ethyl alcohol (25 parts) and water (50 parts) to form asmooth paste. To this paste was added Turkeyv red oil (10 parts) andisopropylated naphthalene-beta-sultonic acid (1.5 parts). This mixturewas agitated and caustic soda solution (70 parts, 36 B.) was Example IX2 3'-hydroxybenzoylamino-benzene (10 parts) was mixed with Turkey redoil (2.5 parts) and an aqueous solution of isopropylatedbeta-naphthalene-sulfonic-acid (0.8 part in 10 parts of water). Thismixture was stirred to a smooth paste and caustic soda solution (17parts, 36 B.) was added to convert the2':3'-hydroxynaphthoylamino-benzene to its sodium salt. The resultingthick paste was thoroughly mixed and then diluted with an aqueoussolution of sodium carbonate, (1.8 parts in 10 parts of water). Theresulting mixture was further diluted with water (4 parts), agitateduntil uniform, and then dried on a rotary drum drier. The product wascollected as non-dusting flakes which showed excellent wettability andsolubility in cold water.

The usual diazoimino compounds can be employed,examp1es of which are thereaction products of diazo compounds from primary arylamines withsarcosine, proline, and methyl-glucamine. The diazo components arepreferably free from sulfonic and carboxylic acid groups. Examples ofthese primary arylamines are Aniline m-Chloro-aniline2:5-dichloro-aniline 5-chloro-2-amino-toluene 4-chloro-2-amino-anisole 25-dimethoxy-aniline 4-nitro-2-amino-toluene 5-nitro-2-amino-toluene4-n'itro-2-amino-anisole 5-nitro-2-amino-anisole Dianisidine 4-benzo3lamino-2 5-dieth'oxy-aniline -carbomethoxy-amino -2 5 -diethoxy-anilineThe composition of the new compositions other than the ice colorcoupling components may vary widely. Dextrin may be supplemented by canesugar or similar water-soluble carbohydrate material. The ratio ofprotective colloid and diluent to ice color coupling component also mayvary widely, but the preferred-products contain from 20% to 70% of theice color coupling component. As wetting out and dispersing agents,

' finished cry compositions.

' the drying process,

I superiorto-those of aration' of dye baths,

scribed in the present application are stances, the, wetting out agentsremain in the The wet compositions may be converted to virtuallyproducts by evaporation in graining bowls containing heavy duty,agitators. During the materials are" subjected to plastic milling insuch equipment. Alternatively the mixtures may be dried on rotary drumthe alkali metal salts of the ice color coupling components, saidcoupling components being,

s from the group consisting of arylamides of orthoof a dispersing agentand Turkey red; oil alkali,

driers on vacuum tray driers,'or in other suitable equipment. Thecompositions are uniformly constituted and nolack of uniformity isnoticeable in the subdivided products. In order to. ob: ,tain the bestwetting out characteristics in the finished products. the dry materialsshould con,-

tain a small amount of residual moisture usual- 1y less than 2%. Theproducts are virtually.

dry, somewhat porous and friable. They are There,

is no advantage in easily subdivided to a suitable degree of fineness; II and uniformity, 'asby grinding. The subdivided material is granular. Iextremely fine grinding. The grain sizes in the,

preferred products range from approximately 10 1 to 200*mesh' butlargeror smaller grain sizes can be used. j

,j J The new compositions of the-present inven tion are especiallyuseful for baths for padding textile fibers with'the ice color couplingcomponents, such fibers subsequently to'b'e dyed or printed with diazosalts. The dry compositions also maybe mixed with drywater solublediazoimino' compounds, with dry nitro'sthe preparation of Ihydroxy-aryl-ca andcarboxyl 8 3 19 at least a suiilcient mount metalsalt to make a dispersion when the com 1 position is added to water; andan excess of an alkali metal hydroxide over that necessary to form analkali metal'salt of the coupling com- I ponent; said composition beingcharacterized by its property to wet-out rapidly with water, by

being rapidly solublein water, by being nondusting and by stability uponstorage.

I 2. A' virtually dry'flaked non-dusting article of a uniform porousfriable composition which comprises a subdivided compound of a groupconsisting of the alkali metal salts, of the ice' color, couplingcomponents, said coupling components being from the group consisting ofarylamides' I of orthohydroxy arylcarboxylic acids and betaketo-carboxyllc acids which are devoid of sulfonic acid andcarboxylgroups; at least a sufficient amount of dispersing a ent and Turkey redoil alkali metal'salt to make a dis- I persion when the composition isadded to water;

amines (antidiazotates) prepared from arylamines, or with dry 'diazo'sulfonates. to produce mixtures suitable for dyeing and printing. ,SuchI mixtures show advantagesin wetting out and dispersing properties Theproducts of and printing pastes. It is wellknown that the alkali metalsalts of the arylamides of 2:3-hydroxy-naphthoic acid are quite unstableto storage.

sitions containing such alkali metal salts destable.

The dyeing value of the products of the presis observed with the newalso solve another problem of the prior art. Dry

over similar mixtures; con- I taining the ice color couplingcomponentsin'the form of their free ac I I l the present invention are,I the prior art in ease of pre and at least a sumcicnt excess of analkali metal hydroxide over that necessary to form an alkali 1 metalsalt of the coupling component to make the composition soluble' inwater: said cflmposl tion being characterized by being non-dusting.abyaits, property, to wet-out rapidly with water, by

being readily" soluble in water and by stability upon storage.

3. A virtually dry flaked article porous friable 'composition whichcomprises a subdivided alkali metal salt of an arylamide of an ortho'hydroxy --aryl carboxylic acid which is devoid of 'sulfonic' acid andcarbonyl groups; I

. ,suiiicient dispersing agent and Turkey red all However. the compo-.80 tinctorial value and bril- This perhaps may be attributed colorcoupling components, the new products mixtures of the components aredusty and cause textile plants. The

a definite health hazard in and they subdinew compositionsare friablevide into grains without producing nets. 4

From the foregoing disclosure it will be recdusty prqdthat necessary toognized that the invention is susceptible of modi- I flcation withoutdeparting from the spirit and scope thereof and it is to be understoodthat the invention is not restricted to the specific illustrationsthereof herein set forth.

We claim:

1. A virtually dry granular article of a' uniform porous friablecomposition which comprises a subdivided compound or a group consistingof acterized by being acids and beta-keto-carboxylic acids devoid of'sulfonic acid and carboxyl groups; at

alkali metal salt to'make a dispersion when the composition is added towater; and at least a suflicient excess of an alkali metalhydroxide overthat necessary to form an alkali metal salt of the coupling component tomake the composition soluble in water; said composition beingcharacterized by being non-dusting, by its property to wet-outrapidlywith water, by being readily soluble in water and by stabilityupon storage.

4. A virtually dry flaked article of a uniform porous composition whichcomprises a subdivided sodium salt of a 2,3hydroxy-naphthoyl-arylamideof the benzene series which is devoid of sulfonic acid and carboxylgroups; sufllcient of a-dispersing agent and the'sodium salt of Turkeyred oil to make a dispersion when the composition is added to water,said dispersion agent being the condensation product ofnaphthalenebeta-sulfonic acidwith formaldehyde; and at least asufiicient excess of sodium hydroxide over form .the sodium salt of thecoupling component to make the composition soluble in water; saidcomposition being charnon-dusting, by its property to wet-outrapidlywith water and by stability upon storage.-

5. The process which comprises intermixing water; an arylamide of anacid from the group consistingof ortho hydroxy aryl carboxylic which areleast sufllclent of an alkali metal hydroxideto boxylic acids andb'eta'keto-carboxylic acids which are devoid of sulfonic' acid of auniform form an alkali metal salt of said coupling component; at least asufiicient amount of a dispersing agent and the alkali metal salt 01'Turkey red oil to make a dispersion when the virtually dried compositionis added to water; subjecting the mixture to plastic milling until auniform composition is produced; and removing volatile liquidconstituents until the composition is virtually dry and porous andsubdividing the virtually dry porous composition;

6. The process which comprises intermixing water; a volatile liquidorganic wetting agent; an arylamide of anortho-hydroxy-naphthalenecarboxylic acid which is devoid of sulfonicacid and carboxyl groups; an excess of sodium hydroxide over thatnecessary to form the sodium salt of said arylamide; at least asuflicient amount of a dispersing agent and the alkali metal salt ofTurkey r'ed oil to make a dispersion when the virtually driedcomposition is added to Water; subjecting the mixture to plastic millinguntil a uniform composition is produced; and removing volatile liquidconstituents until the composition is virtually dry'and subdividing thevirtually dry composition. v 4

. MJLES A. DAHLEN.

. ARTHUR L. FOX.

